CN111868184B - Copolymer for antifouling paint composition and antifouling paint composition comprising the same - Google Patents
Copolymer for antifouling paint composition and antifouling paint composition comprising the same Download PDFInfo
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- CN111868184B CN111868184B CN201980020125.1A CN201980020125A CN111868184B CN 111868184 B CN111868184 B CN 111868184B CN 201980020125 A CN201980020125 A CN 201980020125A CN 111868184 B CN111868184 B CN 111868184B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
- C09D143/04—Homopolymers or copolymers of monomers containing silicon
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
Abstract
The present invention provides an antifouling paint composition which has good storage stability of paint, and the obtained antifouling paint film does not cause abnormal paint film (whitening, stripping, cracking and the like) in seawater for a long time, and maintains stable paint film solubility and antifouling effect. According to the present invention, there is provided a copolymer for an antifouling paint composition, which is obtained by copolymerizing a mixture of a monomer (a) and a polymerizable unsaturated monomer (b) other than the monomer (a), wherein the monomer (a) is represented by the general formula (1), the monomer (b) contains 2-methoxyethyl methacrylate, the content of the monomer (a) is 5 to 45 mass% based on the total mass of the monomer (a) and the monomer (b), and the content of 2-methoxyethyl methacrylate is 55 to 95 mass% based on the total mass of the monomer (a) and the monomer (b).
Description
[ field of technology ]
The present invention relates to a copolymer for an antifouling paint composition, and an antifouling paint composition comprising the copolymer.
[ background Art ]
Aquatic fouling organisms such as barnacles, dragon worms, mytilus edulis, pergola, sea squirts, enteromorpha, sea lettuce, and silt adhere to underwater structures such as marine vessels (especially, bottom parts), fishing gear such as fishing nets and fishing net accessories, and water pipes for power generation, and cause problems such as functional impairment and appearance impairment of the marine vessels. In particular, in ships, the loss increases against the decrease in speed or the increase in fuel consumption due to the increase.
For this reason, a method of forming an antifouling coating film by applying an antifouling coating material comprising a triorganosilyl copolymer as a carrier to the surface of an underwater structure such as a marine vessel (particularly, a ship bottom portion), a fishing gear such as a fishing net or a fishing net attachment, or a water guide pipe for a power generation system, has been widely used.
The triorganosilyl ester moiety of the triorganosilyl-containing copolymer is hydrolyzed in seawater, and the copolymer gradually dissolves in seawater to renew the surface of the coating film, thereby exerting an antifouling effect.
As the triorganosilyl-containing copolymer, a triorganosilyl-containing copolymer formed by copolymerizing a triorganosilyl ester-containing monomer composed of a branched alkyl group or aryl group such as triisopropylsilyl ester or tert-butyldiphenylsilyl ester and an alkoxyalkyl (meth) acrylate such as 2-methoxyethyl (meth) acrylate has been proposed (patent documents 1 to 4).
However, since the antifouling paint using the triorganosilyl-containing copolymer as a carrier has poor storage stability, it has been proposed to use a dehydrating agent such as ethyl silicate or anhydrite in a paint by mixing the same (patent documents 5 to 6), but this is insufficient, and there is a problem that the storage stability is deteriorated when the humidity at the time of paint production is high.
Further, these triorganosilyl group-containing copolymers have the following problems: the initial coating film is insufficiently dissolved, and the coating film whitens or adheres to fouling organisms during the period of the coating or during the initial parking period.
[ Prior Art literature ]
[ patent literature ]
Japanese patent laid-open No. 7-102193
Japanese patent laid-open No. 2001-226440 (patent document 2)
Japanese patent laid-open publication No. 2005-82725
Japanese patent application 2016-062432
Japanese patent laid-open No. 7-18216
Japanese patent laid-open publication No. 9-48948
[ invention ]
[ problem to be solved by the invention ]
The present invention provides an antifouling paint composition which has good storage stability of paint, and the obtained antifouling paint film does not cause abnormal paint film (whitening, stripping, cracking and the like) in seawater for a long time, and maintains stable paint film solubility and antifouling effect.
[ means for solving the problems ]
According to the present invention, there is provided a copolymer for an antifouling paint composition, which is obtained by copolymerizing a monomer (a) and a mixture of a polymerizable unsaturated monomer (b) other than the monomer (a), wherein the monomer (a) is represented by the general formula (1), the monomer (b) contains 2-methoxyethyl methacrylate, the content of the monomer (a) is 5 to 45 mass% based on the total mass of the monomer (a) and the monomer (b), and the content of 2-methoxyethyl methacrylate is 55 to 95 mass% based on the total mass of the monomer (a) and the monomer (b).
As a result of intensive studies, the present inventors have found that when a copolymer (a) obtained by copolymerizing a specific amount of 2-methoxyethyl methacrylate in a monomer (b) having a specific structure is used as a carrier, an antifouling paint composition which is excellent in paint storage stability even when produced under high humidity conditions, and which does not cause abnormal paint films such as whitening, peeling and cracking in seawater for a long period of time and which is stable for a long period of time can be obtained.
[ detailed description ] of the invention
The present invention will be specifically described below.
1. Antifouling coating composition
The antifouling paint composition of the present invention contains a copolymer (A) for an antifouling paint composition and an antifouling agent (B).
1-1. Copolymer (A) for antifouling paint composition
The copolymer (A) for an antifouling paint composition is a triorganosilyl-containing copolymer obtained by copolymerizing a mixture of the monomers (a) and (b). The copolymer (A) contains monomer units derived from the monomers (a) to (b).
Monomer (a) >, a polymer
The monomer (a) is a triorganosilyl methacrylate monomer represented by the general formula (1).
[ chemical formula 1 ]
(wherein R is 1 Is methyl, R 2 、R 3 、R 4 Is selected from branched alkyl groups having 3 to 8 carbon atoms and phenyl groups which may be the same or different
In the present invention, examples of the monomer (a) represented by the general formula (1) include triisopropylsilyl methacrylate, triisobutylsilyl methacrylate, tri-sec-butylsilyl methacrylate, triisopentylsilyl methacrylate, tri (2-ethylhexyl) silyl methacrylate, triphenylsilyl methacrylate, diisopropylisobutylsilyl methacrylate, diisopropylisoamylsilyl methacrylate, diisopropylsilyl methacrylate, diisopropylcyclohexylsilyl methacrylate, tert-butyldiisopropylsilyl methacrylate, tert-butyldiisobutylsilyl methacrylate, tert-butyldiphenylsilyl methacrylate, and the like, with tert-butyldiphenylsilyl methacrylate and triisopropylsilyl methacrylate being preferred, and triisopropylsilyl methacrylate being particularly preferred. One or two or more of these monomers are used respectively.
Monomer (b) >, a polymer
The monomer (b) is a polymerizable unsaturated monomer other than the monomer (a), and can be copolymerized with the monomer (a). In the present invention, the monomer (b) is required to contain 2-methoxyethyl methacrylate, and the monomer (b) contains a specific amount of 2-methoxyethyl methacrylate, so that the obtained coating composition has the following technical effects: the storage stability is very good, the coating film does not cause abnormal coating film such as whitening, stripping, cracking and the like for a long time, and the coating film solubility and the antifouling effect are stable continuously.
The monomer (b) may contain only 2-methoxyethyl methacrylate or may contain a monomer other than 2-methoxyethyl methacrylate. Examples of the monomer other than 2-methoxyethyl methacrylate include the following monomers.
● Triorganosilyl acrylates such as triisopropylsilyl acrylate, triisobutylsilyl acrylate, tri-sec-butylsilyl acrylate, triisopentylsilyl acrylate, tri (2-ethylhexyl) silyl acrylate, triphenylsilyl acrylate, diisopropylisobutylsilyl acrylate, diisopropylisopentylsilyl acrylate, diisopropyl2-ethylhexyl silyl acrylate, diisopropylphenylsilyl acrylate, diisopropylcyclohexylsilyl acrylate, t-butyldiisopropylsilyl acrylate, t-butyldiisobutylsilyl acrylate, t-butyldiisopentylsilyl acrylate, t-butyldiphenylsilyl acrylate, and the like.
● Methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl acrylate, 2-methoxypropyl (meth) acrylate, 4-methoxybutyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, polyethylene glycol methyl ether (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and the like.
● Zinc versatate (meth) acrylate, magnesium versatate (meth) acrylate, copper versatate (meth) acrylate, zinc octoate (meth) acrylate, magnesium octoate (meth) acrylate, copper octoate (meth) acrylate, zinc laurate (meth) acrylate, magnesium laurate (meth) acrylate, copper laurate (meth) acrylate, zinc stearate (meth) acrylate, magnesium stearate (meth) acrylate, copper stearate (meth) acrylate, and other (meth) acrylic metal side chains, zinc (meth) acrylate, copper (meth) acrylate, and other metal (meth) acrylates.
● Vinyl compounds having functional groups such as vinyl chloride, vinylidene chloride, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl benzoate, vinyl butyric acid, butyl vinyl ether, lauryl vinyl ether, and N-vinylpyrrolidone.
● Aromatic compounds such as styrene, vinyl toluene, and α -methylstyrene.
● Dialkyl ester compounds of unsaturated dibasic acids such as dimethyl malate, dibutyl malate, and dimethyl fumarate.
The copolymerizable monomers other than 2-methoxyethyl methacrylate are used in combination of one or two or more kinds, and are preferably (meth) acrylic esters, particularly preferably methyl (meth) acrylate.
The mass ratio of the content of 2-methoxyethyl methacrylate in the monomer (b) is preferably 0.75 to 0.95, more preferably 0.8 to 0.95, and specifically, for example, 0.75, 0.8, 0.85, 0.9, and 0.95, and may be in a range between any 2 values exemplified herein.
Synthesis of copolymer (A)
The copolymer (A) used for the antifouling paint of the present invention can be obtained by copolymerizing a mixture of the monomer (a) and the monomer (b). The copolymerization is carried out, for example, in the presence of a polymerization initiator.
The content of the monomer (a) in the mixture is 5 to 45% by mass, preferably 10 to 40% by mass, and more preferably 15 to 35% by mass. When the content of the monomer (a) is 5 to 45% by mass, the resulting antifouling paint composition has excellent paint stability, and the paint film does not cause abnormal phenomena such as whitening, peeling and cracking in seawater for a long period of time, and stable paint film solubility and antifouling performance can be maintained from the initial stage. The content is specifically, for example, 5, 10, 15, 20, 25, 30, 35, 40, 45 mass%, and may be in a range between any 2 values exemplified herein.
The content of 2-methoxyethyl methacrylate in the mixture is 55 to 95% by mass, preferably 60 to 90% by mass, and more preferably 60 to 85% by mass. When the content of 2-methoxyethyl methacrylate is 55 to 95 mass%, a coating film formed from the obtained antifouling paint composition has excellent coating film solubility and antifouling effect in seawater from the initial stage, does not cause abnormal coating film such as whitening, peeling and cracking, and can maintain stable coating film solubility and antifouling effect for a long period of time. The content is, for example, specifically 55, 60, 65, 70, 75, 80, 85, 90, 95 mass%, and may be in a range between any 2 values exemplified herein.
The total content of the monomer (a) and 2-methoxyethyl methacrylate is 60 mass% or more, preferably 70 mass% or more, more preferably 80 mass% or more, based on the total mass of the monomer (a) and the monomer (b). Within the above range, coating film abnormality such as whitening, peeling and cracking is not caused, and the coating film solubility is stable for a long period of time, and excellent antifouling effect is exhibited. Specifically, the content is, for example, 60, 65, 70, 75, 80, 85, 90, 95, or 100 mass%, and may be in a range between any 2 values exemplified herein.
The weight average molecular weight of the copolymer of the present invention is preferably 5000 to 300000. This is because if the molecular weight is less than 5000, the coating film of the antifouling paint becomes fragile, peeling or cracking is likely to occur, and if it exceeds 300000, the viscosity of the copolymer solution increases, and handling becomes difficult. The Mw is specifically, for example, 5000, 10000, 20000, 30000, 40000, 50000, 60000, 70000, 80000, 90000, 100000, 200000, 300000, and may be within a range between any 2 values exemplified herein.
Examples of the polymerization initiator include azo compounds such as 2,2' -Azobisisobutyronitrile (AIBN), 2' -azobis-2-methylbutyronitrile, and dimethyl 2,2' -azobisisobutyrate; benzoyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-butyl peroxyisopropyl carbonate, t-butyl peroxy 2-ethylhexanoate, 1, 3-tetramethylbutyl peroxy-2-ethylhexanoate, and the like. These polymerization initiators may be used alone or in combination of 2 or more. As the polymerization initiator, 2' -azobisisobutyronitrile and 1, 3-tetramethylbutyl peroxy-2-ethylhexanoate are particularly preferable.
The molecular weight of the triorganosilyl ester-containing copolymer can be adjusted by appropriately setting the amount of the polymerization initiator used.
Examples of the polymerization method include solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization. Among them, solution polymerization is particularly preferred in view of the capability of simply and precisely obtaining the copolymer (A).
In the above polymerization, an organic solvent may be used as needed. Examples of the organic solvent include aromatic hydrocarbon solvents such as xylene, ethylbenzene, toluene, and the like. Aliphatic hydrocarbon solvents such as hexane and heptane. Ethyl acetate, butyl acetate, isobutyl acetate, methoxypropyl acetate and the like. Alcohol solvents such as isopropyl alcohol and butyl alcohol. Ether solvents such as dioxane, diethyl ether and dibutyl ether. Ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. Among them, an aromatic hydrocarbon solvent is particularly preferable, and xylene is more preferable. These solvents may be used alone or in combination of 2 or more.
The reaction temperature of the polymerization reaction is usually 70 to 120℃and may be appropriately set depending on the kind of the polymerization initiator, and is preferably 70 to 100 ℃. The reaction time of the polymerization reaction may be appropriately set depending on the reaction temperature and the like, and is usually about 4 to 8 hours.
The polymerization reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon.
1-2. Antifouling agent (B)
Examples of the stain-proofing agent (B) include inorganic agents and organic agents.
Examples of the inorganic reagent include cuprous oxide, copper thiocyanate (general name: rhodamine copper), and copper powder. Among them, cuprous oxide and rhodamine copper are particularly preferable, and from the viewpoint of long-term stability during storage, surface treatment of cuprous oxide with glycerin, sucrose, stearic acid, lauric acid, lysine, mineral oil, or the like is more preferable.
Examples of the organic reagent include 2-mercaptopyridine-N-copper oxide (common name: copper pyrithione), 2-mercaptopyridine-N-zinc oxide (common name: zinc pyrithione), zinc ethylenebisdithiocarbamate (common name: zineb), 4, 5-dichloro-2-N-octyl-3-isothiazolone (common name: SEA-NINE 211), 3, 4-dichlorophenyl-N-dimethylurea (common name: diuron), 2-methylsulfanyl-4-tert-butylamino-6-cyclopropylamino-s-triazine (common name: irgarol 1051), 2- (p-chlorophenyl) -3-cyano-4-bromo-5-trifluoromethylpyrrole (common name: ECONEA 28), (+ -) 4- [1- (2, 3-dimethylphenyl) ethyl ] -1H-imidazole (common name: medetomidine), and the like.
These antifouling agents may be used in combination of 1 or 2 or more.
The content of the antifouling agent in the composition of the present invention is not particularly limited, but is usually 0.1 to 75% by mass, preferably 1 to 60% by mass, based on the solid content of the composition of the present invention. When the content of the anti-fouling agent is less than 0.1 mass%, a sufficient anti-fouling effect may not be obtained. When the content of the antifouling agent exceeds 75 mass%, the formed coating film is weak, and the adhesion to the coating film-formed product is also weak, and the function as an antifouling coating film cannot be exhibited.
1-3. Other additives
The resin for the antifouling paint of the invention can be further added with dissolution regulator, plasticizer, pigment, dye, defoamer, dehydrating agent, thixotropic agent and organic solvent as the antifouling paint according to actual needs.
Examples of the elution regulator include rosin, rosin derivatives, naphthenic acid, cycloalkenyl carboxylic acid, bicycloalkenyl carboxylic acid, tertiary carbonic acid, trimethylisobutenyl cyclohexene carboxylic acid, and metal salts, monocarboxylic acids, salts thereof, and alicyclic hydrocarbon resins thereof. These may be used alone or in combination of 2 or more.
Examples of the rosin derivatives include hydrogenated rosin, disproportionated rosin, maleated rosin, formylated rosin, and polymerized rosin. Examples of the alicyclic hydrocarbon resin include Quinton1500, 1525L, 1700 (trade name, manufactured by Nippon Zeon company).
Examples of the plasticizer include phosphates, phthalates, adipates, sebacates, epoxidized soybean oil, alkyl vinyl ether polymers, polyalkylene glycols, t-nonylpentasulfide, vaseline, polybutene, tris (2-ethylhexyl) trimellitate, silicone oil, liquid paraffin, chlorinated paraffin, and the like. These may be used alone or in combination of 2 or more.
Examples of the dehydrating agent include synthetic zeolite adsorbents, silicates such as orthoesters, tetramethoxysilane and tetraethoxysilane, isocyanates, carbodiimides and carbodiimidazoles. These may be used alone or in combination of 2 or more.
2. Method for producing antifouling paint composition
The antifouling paint composition of the present invention can be produced, for example, by mixing and dispersing a mixed solution containing the copolymer, an antifouling agent, other additives and the like by using a dispersing machine.
The above-mentioned mixed solution is preferably a solution in which various materials such as a copolymer and an antifouling agent are dissolved or dispersed in a solvent.
As the above-mentioned dispersing machine, for example, a dispersing machine which can be used as a fine pulverizer can be preferably used. For example, a commercially available homogenizer, a sand mill, a bead mill, or the like can be used. The above-mentioned mixed solution may be mixed and dispersed by using a device in which glass beads for mixing and dispersing are added to a container provided with a stirrer.
3. Stain-proofing treatment method, stain-proofing coating film and coated article
The method for treating an antifouling coating according to the present invention is a method for forming an antifouling coating film on the surface of a coated film-formed article by using the above-mentioned antifouling coating composition. According to the method of the present invention, the antifouling coating film is gradually dissolved from the surface to thereby always renew the surface of the coating film, whereby adhesion of aquatic fouling organisms can be prevented.
Examples of the coating film-forming material include ships (particularly, bottoms), fishing gear, underwater structures, and the like.
The thickness of the antifouling coating film may be appropriately set according to the type of the coating film-formed article, the sailing speed of the ship, the sea water temperature, and the like. For example, when the object to be coated is the bottom of a ship, the thickness of the antifouling coating film is usually 50 to 700. Mu.m, preferably 100 to 600. Mu.m.
[ example ]
The features of the present invention will be further clarified by examples and the like shown below. However, the present invention is not limited to these examples.
The% in each of the production examples, reference examples, examples and comparative examples represents mass%.
The heating residual component was obtained by heating at 125℃for 1 hour based on JIS K5601-1-2 (ISO 3251).
The weight average molecular weight (Mw) is a value (polystyrene equivalent) obtained by GPC.
The conditions for GPC are as follows.
HLC-8220GPC manufactured by Tosoh Co., ltd
column/TSKgel SuperHZM-M (manufactured by Tosoh Co., ltd.) 2 roots
Flow rate 0.35mL/min
Detector RI
Column constant temperature bath temperature 40 DEG C
Eluent. THF
The unit of the mixing amount of each component in the table is g.
Production example 1 (production of copolymer P-1) >)
A2000 ml flask equipped with a thermometer, a reflux condenser, a stirrer and a dropping funnel was charged with 400g of xylene, stirred under a nitrogen atmosphere and heated to 85.+ -. 2 ℃, and a mixture of 175g of triisopropylsilyl methacrylate, 300g of 2-methoxyethyl methacrylate, 25g of methyl methacrylate, and 5g of 1, 3-tetramethylbutylperoxy-2-ethylhexanoate (PEROCTA O, manufactured by Japanese fat and oil) was dropped over 1 hour at 85.+ -. 2 ℃. After the dropping, the polymerization reaction was completed by adding 0.5g of 1, 3-tetramethylbutyl peroxy-2-ethylhexanoate 3 times per hour at 85.+ -. 2 ℃ and then heating to 110 ℃ and cooling for 30 minutes, and 100g of xylene was added at 90 ℃ or lower to dissolve the xylene, thereby obtaining a copolymer solution P-1. The heating residue of P-1 was 49.7%, and the weight-average molecular weight was 52000.
Production examples 2 to 8 and reference examples 1 to 12 >, respectively
The same procedure as in production example 1 was repeated except that the organic solvents, monomers and polymerization initiators shown in tables 1 to 2 were used to obtain copolymer solutions P-2 to P-8 and comparative copolymer solutions H-1 to H-12. The heating residual components and the weight average molecular weight of each of the obtained copolymer solutions were measured. The results are shown in tables 1 to 2.
[ Table 1 ]
TABLE 1
[ Table 2 ]
Examples 1 to 12 and comparative examples 1 to 12 >, respectively
Using the copolymer solutions P-1 to P-8 obtained in production examples 1 to 8 and reference examples 1 to 12 and the copolymer solutions H-1 to H-12 of comparative examples, antifouling paint compositions were prepared by mixing as shown in tables 3 to 4.
(preparation of coating composition)
The antifouling paint compositions of examples 1 to 12 and comparative examples 1 to 12 were prepared by mixing and dispersing them in an air stream having a humidity of 90% or higher using a small bench sand mill for experiment (using glass beads having a diameter of 1.5 to 2.5 mm) for 1 hour by operating 2 humidifiers, and then, the antifouling paint compositions were separated into 2 tin cans of 100ml, and the paint of one tin can was used for various tests of coating films and the paint of the other tin can was used for evaluation of storage stability.
(evaluation of storage stability of coating)
The viscosity of the paint contained in one tin can was measured, and after sealing and storage in a thermostat at 45 ℃ for 3 months, the viscosity of the paint was measured by a type B viscometer.
The evaluation of the storage stability of the paint was performed in the following manner.
And (3) the following materials: the viscosity change of the paint is less than 500 mPa.s/25 ℃ (hardly thickened)
O: the viscosity of the paint changes to 500-5000 mPa.s/25 ℃ (slightly thickened)
Delta: the viscosity change of the paint is more than 5000 mPa.s/25℃ (great thickening)
X: viscosity change to no measurement (gel or solid state)
The results are shown in tables 3 and 4.
(measurement of hardness of coating film)
The film hardness of the coating was measured using a Pendulum (penduloum) durometer.
Each of the paint samples was applied to a release plate (100×200×2 mm) so that the thickness after drying was about 100 μm, and after drying at 40 ℃ for 1 day, the hardness of the coating film was measured by a pendulum type durometer in a room at 25 ℃. The value is a count.
The results are shown in tables 3 and 4.
(rotation test)
A rotary drum of 515mm diameter and 440mm height was mounted in the center of the trough and rotated by a motor. In addition, a cooling device for keeping the temperature of the seawater constant and a pH automatic controller for keeping the pH of the seawater constant are installed.
Test panels were made as follows.
First, a rust-preventive coating material (epoxy vinyl-based A/C) was applied to a titanium plate (71X 100X 0.5 mm) so that the thickness after drying was about 100. Mu.m, and dried, whereby a rust-preventive coating film was formed. Next, the coating compositions obtained in examples 1 to 12 and comparative examples 1 to 12 were applied to the rust inhibitive coating films so that the thickness after drying was about 300 μm. The resulting coated material was dried at 40℃for 3 days, thereby producing a test plate having a dried coating film with a thickness of about 300. Mu.m.
The test plate thus produced was fixed to a rotating drum of a rotating apparatus of the above apparatus so as to be in contact with seawater, and the rotating drum was rotated at a speed of 20 knots. The temperature of the seawater is kept at 25 ℃ and the pH is kept at 8.0-8.2, and the seawater is replaced once a week.
● Measurement of coating film solubility
The residual film thickness of each test plate was measured at the beginning of the test and every 1 month after the start of the test by using a shape measuring laser microscope VK-X100 manufactured by KEYENCE, and the dissolved film thickness was calculated from the difference, thereby obtaining the film dissolution amount (μm/month) every 1 month.
The results are shown in tables 3 and 4.
● Observation of surface State of coating film
In the measurement of the residual film thickness after the spin test for 6 months, the surface of each coating film was observed with naked eyes and a microscope, and the surface state of the coating film was evaluated.
The evaluation of the surface state of the coating film was performed according to the following criteria.
Excellent and completely free of abnormalities
Observation of a few hairline cracks
Delta is that capillary cracks are observed on the whole surface of the coating film
X, abnormal coating such as cracks, bubbles, peeling and the like was observed
The results are shown in tables 3 and 4.
● Whitening observation of coating film
In the measurement of the residual film thickness after the rotation test for 6 months, the presence or absence of whitening on the surface of each coating film was evaluated with naked eyes.
The presence or absence of whitening of the coating film surface by the naked eye was evaluated according to the following criteria.
O: the color of the coating film surface is hardly changed
Delta: the color of the coating film surface was slightly whitened
X: general color whitening of the coating film
The results are shown in tables 3 and 4.
● L value measurement of coating film
The L value (brightness) was measured by a colorimeter for the coating film before the spin test and the residual coating film after 6 months of the spin test. Color Meter ZE6000 manufactured by Nippon electric Color industry Co., ltd. The L value (luminance) is a value defined in JIS Z8781-4 (formula in CIE system). Since white is 100 and black is 0 in the L value (luminance), when the surface of the coating film whitens, the coating film becomes bright and the number of the L value increases.
(antifouling test (static immersion test))
The antifouling paint obtained in each of examples 1 to 12 and comparative examples 1 to 12 was applied to both surfaces of a rigid polyvinyl chloride plate (100X 200X 2 mm) so that the thickness of the film as a dried film was about 200. Mu.m. The test plate was immersed 1.5m below the sea surface of the Convergence of Tri county, the observation was made for 12 months and the fouling of the test plate by the attached organisms was evaluated. The evaluation was performed by visually observing the state of the surface of the coating film, and was judged according to the following criteria.
Very good, no attachment of fouling organisms such as shellfish and algae and almost no sludge.
No fouling organisms such as shellfish and algae, and a small amount of sludge (the extent of visible coating surface) were adhered, and the scale was removed by gentle wiping with a brush.
Delta is a grade that no fouling organisms such as shellfish and algae adhere, but the sludge adheres thickly to such an extent that the surface of the coating film is not clearly seen and cannot be removed even by strong wiping with a brush.
Table 3 and Table 4 show the results of the scale of fouling organisms such as shellfish and algae.
[ Table 3 ]
TABLE 3 Table 3
[ Table 4 ]
TABLE 4 Table 4
The antifouling agents, pigments and other additives shown in tables 3 and 4 are specifically as follows.
< antifouling Agents >
Cuprous oxide (manufactured by NISSHIN CHEMCO Co., ltd., NC-301 average particle diameter 3 μm)
Copper pyrithione (manufactured by Arch Chemicals Co., ltd., copper Omadine)
Pigment >, pigment
Iron oxide red (TODA Pigment manufacturing, TODA COLOR EP-13D)
Talc (CROWNTALC 3S manufactured by Songcun industry)
Zinc oxide (manufactured by Zhengshi chemical Co., ltd., zinc oxide 2 kinds (trade name))
Titanium oxide (ancient river machinery metal manufacturing, FR-41)
< other additives >)
Tetraethoxysilane (KISHIDA chemical manufacturing, reagent grade)
Rosin zinc salt (50% xylene solution)
Chlorinated paraffin (trade name "EMPARA A-40S", manufactured by Tosoh Co., ltd.)
DISPARON A603-20X (thixotropic agent of fatty acid amide series manufactured by Nanzhu chemical industry)
From tables 3 and 4, it can be seen that: the coating materials produced using the coating compositions of the present invention (examples 1 to 12) were excellent in storage stability, and the amount of the coating film formed dissolved in seawater was maintained at a high level, and there was little adhesion of fouling organisms such as shellfish and algae and little adhesion of sludge in the antifouling test. The state of the dried coating film after the spin test for 6 months was also satisfactory without abnormalities such as whitening, cracking, peeling, and the like.
In contrast, the coating materials produced using the coating compositions of comparative examples 1 to 6 or 10 to 12 were inferior in storage stability to the examples, and the coating film formed using the coating materials was liable to be whitened.
The coating materials produced using the coating compositions of comparative examples 7 to 9 had low dissolution in seawater, and insufficient prevention of attachment of fouling organisms.
Claims (3)
1. A copolymer for an antifouling paint composition, which is obtained by copolymerizing a mixture of a monomer (a) and a polymerizable unsaturated monomer (b) other than the monomer (a),
the monomer (a) is represented by the general formula (1),
the monomer (b) contains 2-methoxyethyl methacrylate,
the content of the monomer (a) occupies 5 to 45 mass% in the total mass of the monomer (a) and the monomer (b),
the content of 2-methoxyethyl methacrylate is 55 to 95 mass% based on the total mass of the monomer (a) and the monomer (b),
[ chemical formula 1 ]
Wherein R is 1 Is methyl, R 2 、R 3 、R 4 Is selected from branched alkyl groups having 3 to 8 carbon atoms and phenyl groups, and is the same or different.
2. The copolymer according to claim 1, wherein,
the total content of the monomer (a) and 2-methoxyethyl methacrylate occupies 70 mass% or more of the total mass of the monomer (a) and the monomer (b).
3. An antifouling paint composition comprising a copolymer and an antifouling agent,
the copolymer is a copolymer for an antifouling paint composition according to claim 1 or claim 2.
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| JP2018-080026 | 2018-04-18 | ||
| JP2018080026 | 2018-04-18 | ||
| PCT/JP2019/015971 WO2019203154A1 (en) | 2018-04-18 | 2019-04-12 | Copolymer for stain-proof coating compositions, and stain-proof coating composition containing said copolymer |
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| JP3261220B2 (en) | 1993-06-30 | 2002-02-25 | 日本油脂ビーエーエスエフコーティングス株式会社 | Underwater antifouling paint composition |
| JP2790021B2 (en) | 1993-09-30 | 1998-08-27 | 日本油脂株式会社 | Paint composition |
| JP3696333B2 (en) | 1995-06-01 | 2005-09-14 | 中国塗料株式会社 | Antifouling coating composition, coating film formed from the antifouling coating composition, antifouling method using the antifouling coating composition, and hull or underwater structure coated with the coating |
| JP3857010B2 (en) | 2000-02-17 | 2006-12-13 | 日本ペイント株式会社 | Copolymer and coating composition |
| EP1277816B1 (en) * | 2000-04-24 | 2006-11-08 | BASF Coatings Japan Ltd. | Antifouling coating material, antifouling coating film, submerged structure, and antifouling method |
| JP4064100B2 (en) * | 2001-12-13 | 2008-03-19 | 日東化成株式会社 | Anti-fouling composition for fishing nets, fishing nets coated with the anti-fouling composition for fishing nets, and anti-fouling method for fishing nets using the anti-fouling composition for fishing nets |
| US20030225184A1 (en) * | 2002-05-30 | 2003-12-04 | Aubart Mark Anthony | Triarylsilyl(meth)acryloyl-containing polymers for marine coating compositions |
| JP2005082725A (en) * | 2003-09-09 | 2005-03-31 | Nitto Kasei Co Ltd | Antifouling coating composition and submarine articles coated with the composition, and antifouling method using the composition |
| EP2128208B1 (en) * | 2007-02-27 | 2012-08-08 | Nitto Kasei Co., Ltd. | Stain-proof coating composition, method for production of the composition, stain-proof coating film formed by using the composition, coated article having the coating film on the surface, and stain-proofing treatment method for forming the coating film |
| JP5142150B2 (en) * | 2008-10-02 | 2013-02-13 | Ｎｋｍコーティングス株式会社 | Copolymer composition, antifouling paint composition, construction method and structure |
| JP4521589B2 (en) * | 2008-12-19 | 2010-08-11 | 日東化成株式会社 | Antifouling paint composition, antifouling coating film formed using the composition, coated product having the coating film on the surface, and antifouling treatment method for forming the coating film |
| JP6217576B2 (en) | 2014-09-19 | 2017-10-25 | 京セラドキュメントソリューションズ株式会社 | Image forming apparatus and screen operation method |
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